CN101891974A - Method for preparing TiO2/SiO2 composite powder - Google Patents

Method for preparing TiO2/SiO2 composite powder Download PDF

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CN101891974A
CN101891974A CN 201010232209 CN201010232209A CN101891974A CN 101891974 A CN101891974 A CN 101891974A CN 201010232209 CN201010232209 CN 201010232209 CN 201010232209 A CN201010232209 A CN 201010232209A CN 101891974 A CN101891974 A CN 101891974A
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tio
sio
wet gel
xerogel
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CN101891974B (en
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伍媛婷
王秀峰
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a method for preparing TiO2/SiO2 composite powder, which comprises the following steps of: preparing wet gel from ethanol serving as a solvent, a citric acid serving as a complex and polyethylene glycol serving as a dispersant, and drying, foaming and calcining the wet gel to prepare submicron TiO2 spheres; and dispersing the submicron TiO2 spheres in SiO2-containing sol A, performing water-bath evaporation, drying and foaming with stirring to composite TiO2 and SiO2, and finally calcining the mixture to prepare the TiO2/SiO2 composite powder. The method of the invention has the advantage of short preparation period, and the prepared TiO2/SiO2 composite microspheres have the integrated sphericity of 0.5 to 2 mu m, and high purity and yield.

Description

A kind of TiO 2/ SiO 2The preparation method of composite granule
Technical field
The invention belongs to technical field of nano material, relate to a kind of TiO 2/ SiO 2The preparation method of composite granule.
Background technology
Characteristics such as that titanium dioxide has is nontoxic, harmless, chemical stability is high, opaque, whiteness and glossiness excellence and photocatalytic activity are good, be a kind of good white inorganic pigment and photocatalyst, but because the titanium dioxide energy gap is big, need under near-ultraviolet light, just can excite the generation electron-hole pair, less to the sunlight utilization ratio, and exist easily assemble, easily inactivation, be difficult to shortcoming such as recycling.In addition,, when using, easily cause phenomenons such as paint film xanthochromia, efflorescence as coating because there is too strong photocatalytic in titanium dioxide, and TiO 2/ SiO 2Composite granule be able to improve these defectives, thereby widens the application of titanium dioxide.
Present TiO 2/ SiO 2The preparation method of matrix material comprises sol-gel method, coprecipitation method, chemical vapour deposition etc.Though chemical Vapor deposition process has short, advantage, its TiO such as cost is lower of cycle 2/ SiO 2Composite material granular exist the size distribution broad, inhomogeneous, Si/Ti is difficult to mix than wayward and component and cause shortcomings such as the product chemical constitution is inhomogeneous.The shortcoming of traditional sol-gel method is that cost is higher, treatment temp is higher, the easy reunion of progenitor grows up.Coprecipitation method production efficiency is lower, and product is difficult for separating controlling, and impurity is more.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of TiO 2/ SiO 2The preparation method of composite granule, this method production technique is simple, the cycle is short, equipment is simple, prepared TiO 2/ SiO 2Composite granule is a spherical particle, regular shape, better dispersed.
The present invention is achieved through the following technical solutions:
A kind of TiO 2/ SiO 2The preparation method of composite granule may further comprise the steps:
1) with deionized water and dehydrated alcohol by 1.5～2: 1 volume ratio is made into ethanolic soln; The ratio that adds 12～17g citric acid, 2～3ml butyl (tetra) titanate and 3.5～5.6g polyoxyethylene glycol then in the 100ml ethanolic soln, the preparation mixing solutions;
Mixing solutions is evaporated to 80～90 ℃ of water-baths obtains wet gel, then with wet gel at 130 ℃～140 ℃ dry down foaming 3～6h, form xerogel; Again xerogel is obtained TiO behind calcining 2～6h down at 600～900 ℃ 2Sub-micron ball;
2) citric acid is dissolved in the ammoniacal liquor, the amount of ammoniacal liquor is as the criterion can dissolve citric acid, and then according to tetraethoxy: the mol ratio of citric acid=1: 1.5～2 adds tetraethoxy, stirs to make the tetraethoxy dissolving; After waiting to dissolve, add the dehydrated alcohol of ammoniacal liquor volume 1/3～1/2 and the polyoxyethylene glycol of citric acid quality 1/3～1/2 more successively, be heated to 50～60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0～8.0 with ammoniacal liquor, obtain Sol A;
3) be Si: Ti=1 according to mol ratio: 5～7 ratio, with TiO 2The sub-micron ball ultra-sonic dispersion is in Sol A, and 80～90 ℃ of water-bath evaporations under agitation are until obtaining wet gel B after disperseing to finish;
4) wet gel B obtains xerogel behind 130～140 ℃ of dry foaming 3～5h, and xerogel is carried out calcining at constant temperature at 600～700 ℃, takes out behind calcining 3～5h, obtains TiO 2/ SiO 2Composite granule.
Described ammoniacal liquor is that volumetric concentration is 25～28% ammoniacal liquor.
The molecular weight of described polyoxyethylene glycol is 4000 or 6000.
Described wet gel carries out the drying foaming under air atmosphere.
Described xerogel carries out calcining at constant temperature under air atmosphere.
Compared with prior art, the present invention has following beneficial technical effects:
The present invention is solvent with the butyl (tetra) titanate raw material with ethanol, is complexing agent with the citric acid, and polyoxyethylene glycol is a dispersion agent, makes wet gel, obtains TiO after drying, foaming, the calcining again 2Sub-micron ball; With TiO 2The sub-micron ball ultra-sonic dispersion makes siliceous xerogel be coated on dispersive TiO in the process of the evaporation of water-bath under agitation, drying, foaming in Sol A 2The sub-micron ball surface makes TiO after the calcining at last 2/ SiO 2Composite granule.The TiO of gained 2/ SiO 2Complex microsphere is the full spherical of 0.5～2 μ m for size, TiO 2Be the core of spherical particle, SiO 2Be compounded in and form TiO on every side 2/ SiO 2Complex microsphere.And, prepared TiO 2/ SiO 2Composite granule does not influence TiO 2Katalysis, and because circumgranular SiO 2Compound, make composite particles that hard poly-group be difficult for take place.
In addition, TiO of the present invention 2/ SiO 2There is not impurity such as introducing chlorion in composite granule in this preparation process, need not the suction filtration cleaning to remove impurity, can shorten preparation cycle; Employed complex compound citric acid, polyoxyethylene glycol and raw material are introduced in preparation is organic substance, can remove fully when calcining, and tetraethoxy, butyl (tetra) titanate is with whole converted products prepared TiO 2/ SiO 2The purity height of composite granule, better dispersed, even particle size, complete shape and appearance, yield rate height.
Description of drawings
Fig. 1 is the TiO of the present invention's preparation 2/ SiO 2The SEM photo of complex microsphere, TiO as can be seen 2/ SiO 2The particle of composite granule is the sphere of complete shape and appearance, and granular size is 0.5～2 μ m.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done to describe in further detail, the explanation of the invention is not limited.
Embodiment 1
A kind of TiO 2/ SiO 2The preparation method of composite granule may further comprise the steps:
1) deionized water and dehydrated alcohol are made into ethanolic soln by 1.5: 1 volume ratio; Get the 100ml ethanolic soln then and add 12g citric acid, 2ml butyl (tetra) titanate and 3.5g polyoxyethylene glycol, the preparation mixing solutions;
With mixing solutions in 80 ℃ of water-baths evaporation until to the wet gel that obtains white, then with wet gel at 130 ℃ of dry down foaming 6h, the xerogel of formation brownish black; Again xerogel is obtained TiO behind the calcining 6h down at 600 ℃ 2Sub-micron ball;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 300ml ammoniacal liquor, adds the tetraethoxy of 0.5mol then, stirs to make the tetraethoxy dissolving; After waiting to dissolve, add the dehydrated alcohol of 100ml and the polyoxyethylene glycol of 64.05g (PEG4000) more successively, be heated to 50 ℃ of stirrings it is dissolved fully; Transfer pH value to 8.0 with ammoniacal liquor, obtain Sol A;
3) be Si: Ti=1 according to mol ratio: 5 ratio, with TiO 2The sub-micron ball ultra-sonic dispersion after disperseing to finish, evaporates Sol A 80 ℃ of water-baths under agitation until obtaining wet gel B in Sol A;
4) wet gel B obtains xerogel behind 130 ℃ of dry foaming 3h, and xerogel is carried out calcining at constant temperature at 600 ℃, takes out behind the calcining 5h, obtains TiO 2/ SiO 2Composite granule.
Embodiment 2
A kind of TiO 2/ SiO 2The preparation method of composite granule may further comprise the steps:
1) deionized water and dehydrated alcohol are made into ethanolic soln by 2: 1 volume ratio; Get the 100ml ethanolic soln then and add 17g citric acid, 3ml butyl (tetra) titanate and 5.6g polyoxyethylene glycol, the preparation mixing solutions;
With mixing solutions in 90 ℃ of water-baths evaporation until to the wet gel that obtains white, then with wet gel at 140 ℃ of dry down foaming 3h, the xerogel of formation brownish black; Again xerogel is obtained TiO behind the calcining 2h down at 900 ℃ 2Sub-micron ball;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the tetraethoxy of 0.67mol then, stirs to make the tetraethoxy dissolving; After waiting to dissolve, add the dehydrated alcohol of 150ml and the polyoxyethylene glycol of 96.07g (PEG4000) more successively, be heated to 60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0 with ammoniacal liquor, obtain Sol A;
3) be Si: Ti=1 according to mol ratio: 7 ratio, with TiO 2The sub-micron ball ultra-sonic dispersion after disperseing to finish, evaporates Sol A 90 ℃ of water-baths under agitation until obtaining wet gel B in Sol A;
4) wet gel B obtains xerogel behind 140 ℃ of dry foaming 5h, and xerogel is carried out calcining at constant temperature at 700 ℃, takes out behind the calcining 3h, obtains TiO 2/ SiO 2Composite granule.
Embodiment 3
A kind of TiO 2/ SiO 2The preparation method of composite granule may further comprise the steps:
1) deionized water and dehydrated alcohol are made into ethanolic soln by 1.6: 1 volume ratio; Get the 100ml ethanolic soln then and add 15g citric acid, 2.5ml butyl (tetra) titanate and 5.0g polyoxyethylene glycol, the preparation mixing solutions;
With mixing solutions in 85 ℃ of water-baths evaporation until to the wet gel that obtains white, then with wet gel at 135 ℃ of dry down foaming 5h, the xerogel of formation brownish black; Again xerogel is obtained TiO behind the calcining 4h down at 800 ℃ 2Sub-micron ball;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 28% the 300ml ammoniacal liquor, adds the tetraethoxy of 0.62mol then, stirs to make the tetraethoxy dissolving; After waiting to dissolve, add the dehydrated alcohol of 120ml and the polyoxyethylene glycol of 80g (PEG4000) more successively, be heated to 60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.2 with ammoniacal liquor, obtain Sol A;
3) be Si: Ti=1 according to mol ratio: 6 ratio, with TiO 2The sub-micron ball ultra-sonic dispersion after disperseing to finish, evaporates Sol A 82 ℃ of water-baths under agitation until obtaining wet gel B in Sol A;
4) wet gel B obtains xerogel behind 132 ℃ of dry foaming 4h, and xerogel is carried out calcining at constant temperature at 650 ℃, takes out behind the calcining 3.5h, obtains TiO 2/ SiO 2Composite granule.
Embodiment 4
A kind of TiO 2/ SiO 2The preparation method of composite granule may further comprise the steps:
1) deionized water and dehydrated alcohol are made into ethanolic soln by 1.8: 1 volume ratio; Get the 100ml ethanolic soln then and add 16g citric acid, 2.2ml butyl (tetra) titanate and 4.5g polyoxyethylene glycol, the preparation mixing solutions;
With mixing solutions in 86 ℃ of water-baths evaporation until to the wet gel that obtains white, then with wet gel at 138 ℃ of dry down foaming 4h, the xerogel of formation brownish black; Again xerogel is obtained TiO behind the calcining 3.5h down at 680 ℃ 2Sub-micron ball;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 300ml ammoniacal liquor, adds the tetraethoxy of 0.55mol then, stirs to make the tetraethoxy dissolving; After waiting to dissolve, add the dehydrated alcohol of 125ml and the polyoxyethylene glycol of 75g (PEG4000) more successively, be heated to 60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.4 with ammoniacal liquor, obtain Sol A;
3) be Si: Ti=1 according to mol ratio: 6.5 ratio, with TiO 2The sub-micron ball ultra-sonic dispersion after disperseing to finish, evaporates Sol A 85 ℃ of water-baths under agitation until obtaining wet gel B in Sol A;
4) wet gel B obtains xerogel behind 135 ℃ of dry foaming 3.8h, and xerogel is carried out calcining at constant temperature at 620 ℃, takes out behind the calcining 4.5h, obtains TiO 2/ SiO 2Composite granule.
Embodiment 5
A kind of TiO 2/ SiO 2The preparation method of composite granule may further comprise the steps:
1) deionized water and dehydrated alcohol are made into ethanolic soln by 2: 1 volume ratio; Get the 100ml ethanolic soln then and add 12.5g citric acid, 2.4ml butyl (tetra) titanate and 5.2g polyoxyethylene glycol, the preparation mixing solutions;
With mixing solutions in 82 ℃ of water-baths evaporation until to the wet gel that obtains white, then with wet gel at 133 ℃ of dry down foaming 5h, the xerogel of formation brownish black; Again xerogel is obtained TiO behind the calcining 4h down at 720 ℃ 2Sub-micron ball;
2) citric acid 192.14g (1mol) being dissolved in volumetric concentration is in 25% the 300ml ammoniacal liquor, adds the tetraethoxy of 0.50mol then, stirs to make the tetraethoxy dissolving; After waiting to dissolve, add the dehydrated alcohol of 125ml and the polyoxyethylene glycol of 70g (PEG4000) more successively, be heated to 60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.6 with ammoniacal liquor, obtain Sol A;
3) be Si: Ti=1 according to mol ratio: 5.5 ratio, with TiO 2The sub-micron ball ultra-sonic dispersion after disperseing to finish, evaporates Sol A 85 ℃ of water-baths under agitation until obtaining wet gel B in Sol A;
4) wet gel B obtains xerogel behind 132 ℃ of dry foaming 3.4h, and xerogel is carried out calcining at constant temperature at 660 ℃, takes out behind the calcining 4h, obtains TiO 2/ SiO 2Composite granule.

Claims (5)

1. TiO 2/ SiO 2The preparation method of composite granule is characterized in that, may further comprise the steps:
1) with deionized water and dehydrated alcohol by 1.5～2: 1 volume ratio is made into ethanolic soln; The ratio that adds 12～17g citric acid, 2～3ml butyl (tetra) titanate and 3.5～5.6g polyoxyethylene glycol then in the 100ml ethanolic soln, the preparation mixing solutions;
Mixing solutions is evaporated to 80～90 ℃ of water-baths obtains wet gel, then with wet gel at 130 ℃～140 ℃ dry down foaming 3～6h, form xerogel; Again xerogel is obtained TiO behind calcining 2～6h down at 600～900 ℃ 2Sub-micron ball;
2) citric acid is dissolved in the ammoniacal liquor, the amount of ammoniacal liquor is as the criterion can dissolve citric acid, and then according to tetraethoxy: the mol ratio of citric acid=1: 1.5～2 adds tetraethoxy, stirs to make the tetraethoxy dissolving; After waiting to dissolve, add the dehydrated alcohol of ammoniacal liquor volume 1/3～1/2 and the polyoxyethylene glycol of citric acid quality 1/3～1/2 more successively, be heated to 50～60 ℃ of stirrings it is dissolved fully; Transfer pH value to 7.0～8.0 with ammoniacal liquor, obtain Sol A;
3) be Si: Ti=1 according to mol ratio: 5～7 ratio, with TiO 2The sub-micron ball ultra-sonic dispersion is in Sol A, and 80～90 ℃ of water-bath evaporations under agitation are until obtaining wet gel B after disperseing to finish;
4) wet gel B obtains xerogel behind 130～140 ℃ of dry foaming 3～5h, and xerogel is carried out calcining at constant temperature at 600～700 ℃, takes out behind calcining 3～5h, obtains TiO 2/ SiO 2Composite granule.
2. TiO as claimed in claim 1 2/ SiO 2The preparation method of composite granule is characterized in that, described ammoniacal liquor is that volumetric concentration is 25～28% ammoniacal liquor.
3. TiO as claimed in claim 1 2/ SiO 2The preparation method of composite granule is characterized in that, the molecular weight of described polyoxyethylene glycol is 4000 or 6000.
4. TiO as claimed in claim 1 2/ SiO 2The preparation method of composite granule is characterized in that, described wet gel carries out the drying foaming under air atmosphere.
5. TiO as claimed in claim 1 2/ SiO 2The preparation method of composite granule is characterized in that, described xerogel carries out calcining at constant temperature under air atmosphere.
CN2010102322092A 2010-07-21 2010-07-21 Method for preparing TiO2/SiO2 composite powder Expired - Fee Related CN101891974B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993816A (en) * 2012-10-26 2013-03-27 雅安百图高新材料有限公司 Titanium dioxide spherical composite oxide and preparation method thereof
CN103059634A (en) * 2013-01-15 2013-04-24 雅安百图高新材料有限公司 Titanium dioxide silicon dioxide composite oxide powder and preparation method thereof
CN104772132A (en) * 2014-01-13 2015-07-15 唐伯明 Novel SiO2/TiO2 photocatalytic composite powder preparation method
CN105944705A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of TiO2-SiO2 porous material
CN105944706A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of SiO2-TiO2 porous material
CN105964235A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of porous titanium dioxide-silica block
CN114832803A (en) * 2022-04-08 2022-08-02 重庆城市综合交通枢纽（集团）有限公司 Film-forming composition, preparation method thereof and application of composite photocatalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06136290A (en) * 1992-10-27 1994-05-17 Seika Sangyo Kk Production of modified inorganic powder
CN1244516A (en) * 1999-08-10 2000-02-16 复旦大学 Preparation of composite nanometer titania-silica material
CN1342730A (en) * 2001-10-24 2002-04-03 中国科学院大连化学物理研究所 Process for preparing Ti-base composite oxide powder
CN1578813A (en) * 2001-11-01 2005-02-09 纳幕尔杜邦公司 Easy to disperse, high durability TiO2 pigment and method of making same
CN101613537A (en) * 2009-07-31 2009-12-30 孝感学院 A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide
CN101775239A (en) * 2009-01-09 2010-07-14 中国矿业大学(北京) Preparation method of inorganic composite white pigment with high covering power

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06136290A (en) * 1992-10-27 1994-05-17 Seika Sangyo Kk Production of modified inorganic powder
CN1244516A (en) * 1999-08-10 2000-02-16 复旦大学 Preparation of composite nanometer titania-silica material
CN1342730A (en) * 2001-10-24 2002-04-03 中国科学院大连化学物理研究所 Process for preparing Ti-base composite oxide powder
CN1578813A (en) * 2001-11-01 2005-02-09 纳幕尔杜邦公司 Easy to disperse, high durability TiO2 pigment and method of making same
CN101775239A (en) * 2009-01-09 2010-07-14 中国矿业大学(北京) Preparation method of inorganic composite white pigment with high covering power
CN101613537A (en) * 2009-07-31 2009-12-30 孝感学院 A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993816A (en) * 2012-10-26 2013-03-27 雅安百图高新材料有限公司 Titanium dioxide spherical composite oxide and preparation method thereof
CN102993816B (en) * 2012-10-26 2015-01-21 雅安百图高新材料有限公司 Titanium dioxide spherical composite oxide and preparation method thereof
CN103059634A (en) * 2013-01-15 2013-04-24 雅安百图高新材料有限公司 Titanium dioxide silicon dioxide composite oxide powder and preparation method thereof
CN104772132A (en) * 2014-01-13 2015-07-15 唐伯明 Novel SiO2/TiO2 photocatalytic composite powder preparation method
CN104772132B (en) * 2014-01-13 2018-07-20 重庆交通大学 A kind of SiO2/TiO2The preparation method of photocatalysis composite granule
CN105944705A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of TiO2-SiO2 porous material
CN105944706A (en) * 2016-05-05 2016-09-21 陕西科技大学 Preparation method of SiO2-TiO2 porous material
CN105964235A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of porous titanium dioxide-silica block
CN105944706B (en) * 2016-05-05 2018-09-18 陕西科技大学 A kind of SiO2-TiO2The preparation method of porous material
CN105944705B (en) * 2016-05-05 2018-09-18 陕西科技大学 A kind of TiO2-SiO2The preparation method of porous material
CN105964235B (en) * 2016-05-05 2018-09-18 陕西科技大学 A kind of preparation method of poriferous titanium dioxide-silica bulk
CN114832803A (en) * 2022-04-08 2022-08-02 重庆城市综合交通枢纽（集团）有限公司 Film-forming composition, preparation method thereof and application of composite photocatalyst

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